Sulfonium methosulfates



Patented Jan.-25, 1949 2,460,223

- NITE STATES PATENT OFFICE A 2,460,223: I

SULFONIUM METHOSULFATES John N. Hansen, Albert Lea,"Minn., assignortoTheDow Chemical Company, Midland, "Mich,

a-corporation Alf-Delaware NoDrawing, Application. Septemberv 10, 1947,

Serial No. 773,302

:4 =Claims. (Cl. 260-457) 1 Thisinventionrelatesto new sulfoniummethounder refiuxifor 22'-hours.f The'major: proportion sulfatecompounds and particularly those having of the ethanol was thenrecovered by fractional the following general formuladistillationunder-reduced pressuraand-the resi- CH3 CH3 due from thedistillation operation diluted with g R 5 water to dissolve precipitatedsodium chloride. i O-GH OH O-CH CHT- I The-mixture ,was'thenextracted'with-benzene and O H 0 the benzene "distilled oil torecover asa residue l v i 421 grams of normalbutyl beta-(2ephenyl-a1pha- 6phenylethylphenoxy)-ethoxy ethyl sulfide as 'a ll) straw colored viscousoil.

i 86.8 grams (0.2 mol) l or this sulfide and 25.2 wherein Rlreprevsuentsan} alkyl group containing grams (0'.2mol)"of dimethyl'sulfate werereacted zjsoreearbonatems. he v e ing at 70 0- f h s- .T Repre'sentativemembers of the aboveiiderltlfied crude c i -p oduct Wasflissolved'in a,small group of compounds have been prepared and 9111101111? o'f'ethanol,and thereaftendiluted With found tobe viscous oils characterized'byaforyfi othrow-outof'solution the sulfotunate combination of properties inthat they 'nium reaction r ct; is-'oiiy product was aresoluble-in water,of high germicidal and baee te y dc aritafion, washed with diethyltericidal e'flectiveness, substantially odorless, of ether; and warmedunder r du d p ssure to low volatility, stable, and relativelynon-irritatremove traces n -Y'F m't operations, ing to the skinof'humans and animals. These there" a Obtained e 'o o butyl compoundshave been found valuable for the conmethyl: fifl y p p y y p w 1 1 ofmicroorganisms. noxy)-ethoXy-ethyl sulfonium methosulfate as a The newcompounds are cgnveniently prepared straw colored viscous oil completelysoluble in by reacting an ethyl, propyl or butyl mercaptan Water andethanol and relatively insoluble in with beta (2 phenyl alphaphenylethylphediethyl ethernoxy)-beta-chloro-diethyl ether to form a sul- Example 2fide of the formula In a similar fashion, 190.25 grams (0.5 mol) of beta(2 phenyl alphaphenylethyl phenoxy) OGHaCHaO-CHaOHg-S-Rbeta-chloro-diethyl ether, grams (0.5 mol) of O secondarybutylmercaptan, 20.8 grams (0.5 mol) of sodium hydroxide, 37.5 milliliters ofwater and 500 milliliters of ethanol were reacted together to obtain asa principal product of reaction, 218

grams of secondarybutylbeta-(2-phenyl-alphaphenylethyl-phenoxy)-ethoxy-ethy1 sulfide as awherein R represents ethyl, propyl or butyl. This straw l d free-flowingn,

sulfide is then reacted with dimethyl sulfate to 0 5 grams (025 m l) ofthi ulfide 131,5 obtain the desired compound of the invention 10 gramsof dimethyl sulfate (0.25 mol) were mixed The beta- (2 p yalphaphenylethyl together and heated at C. for 21 hours. Then0Xy)beta'-C l y ether employed as a crude reaction product was thenseparated subreactant herein is described in U. S. Patent No. tantiallyas described i Example 1 t v r 2,29 2 as an O y productboilingat 103.5grams of secondarybutyl methyl beta-(2- C. at 2 millimeters pressure,and having a speclfic phenyl-alphaphenylethyl-phenoxy) -eth0xy-ethylgravity 0f1-14 a sulfonium methosulfate as a light viscous oil Thefollowingexamples illustrate the invention, completely Soluble in Water,relatively insoluble but are not to be construed as limiting: in diethylether, and having good emulsifyingv Example 1 properties. 90 grams (1mol) of normalbutyl mercaptan, 40 59 Example 3 grams (1 mol) of sodiumhydroxide, 3805 grams A similar operation was carried out in which (1mol) of beta-(2-phenylalphaphenylethylnormalpropyl mercaptan wassubstituted for the phenoxy) -beta'-chloro-diethyl ether, millilitersnormalbutyl mercaptan set forth in Example 1. of water and 1 liter ofethanol were mixed to- The reaction mixture of the mercaptan, complexgether and heated to boiling temperature and organic halide, caustic,water, and ethanol was heated to a boiling temperature and under refluxfor 22 hours. The crude product was then treated in the usual manner torecover a quantitative yield of normalpropylbeta-(Z-phenylalphaphenylethyl-phenoxy)-ethoxy-ethyl sulfide as an oilyfree-flowing product.

105 grams (0.25 mol) of this sulfide product was reacted with 31.5 grams(0.25 mol) of dimethyl sulfate by heating at 68-72 C. for 21 hours. Thecrude product of the reaction was then cooled and successively treatedwith ethanol and diethyl ether as described in Example 1 to recover asubstantially quantitative yield of normalpropyl methylbeta-(2-phenyl-alphaphenylethylphenoxy)-ethoxy-ethyl sulfoniummethosulfate as a light yellow viscous oil miscible with water in allproportions, soluble in ethanol, and relatively insoluble in diethylether.

Example 4 0.5 molecular proportionsof isopropyl mercaptan, sodiumhydroxide, and beta-(2-phenylalphaphenylethyl-phenoxy)-ethoxy-ethylchloride were reacted together in the presence of 37.5 milliliters ofwater. and 500 milliliters of ethanol in the manner described inExample 1. The solvent was recovered by fractional distillation and theresidue diluted with water and extracted with benzene in the usualmanner to recover 208.5 grams of the desired isopropyi beta:- (2 phenylalphaphenylethyl phenoxy) ethoxy-ethyl sulfide product as a light yellowviscous oil.

105 grams (0.25 mol) of this sulfide product was then reacted with 31.5grams (0.25 mol) of dimethylsulfate by heating at 68-'72 C. for 21hours. Theproduct of reaction was recovered as described in thepreceding example in the form of 136.5 grams of a viscous straw coloredoil readily soluble in water and ethanol, substantially insoluble indiethyl ether, and consisting essentially of isopropyl methylbeta-(Z-phenyl- 4 alphaphenylethyl-phenoxy) -ethoxy-ethyl sulfoniummethosulfate.

Example 5 A further preparation was made in which 31.0 grams of ethylmereaptan was substituted for the isopropyl mercaptan employed inExample 4. The organic sulfide reactionjproduct was isolated as a strawcolored free-flowing oil. 101.64 grams (0.25 mol) of this sulfide wasthen reacted with 31.5 grams (0.25 mol) of dimethyl sulfate by heatingat 70 C. for 21 hours. The resulting product was a light yellow oilreadily soluble in water and ethanol, difiicultly soluble in diethylether, and consistin essentially of ethyl methyl beta-(2- phenylalphaphenylethyl phenoxy) ethoxyethyl sulfonium methosulfate.

I claim:

1. A compound having the formula No references cited.

